Amine‐Borane Dehydrogenation and Transfer Hydrogenation Catalyzed by α‐Diimine Cobaltates

Anionic alpha-diimine cobalt complexes, such as [K(thf)(1.5){((Dipp)BIAN)Co(eta(4)-cod)}] (1; Dipp=2,6-diisopropylphenyl, cod=1,5-cyclooctadiene), catalyze the dehydrogenation of several amine-boranes. Based on the excellent catalytic properties, an especially effective transfer hydrogenation protocol for challenging olefins, imines, and N-heteroarenes was developed. NH3BH3 was used as a dihydrogen surrogate, which transferred up to two equivalents of H-2 per NH3BH3. Detailed spectroscopic and mechanistic studies are presented, which document the rate determination by acidic protons in the amine-borane